U.S. patent number 4,480,039 [Application Number 06/448,542] was granted by the patent office on 1984-10-30 for heavy oil sample preparation.
This patent grant is currently assigned to Shell Oil Company. Invention is credited to Philip J. Closmann, James T. Wortham.
United States Patent |
4,480,039 |
Closmann , et al. |
October 30, 1984 |
Heavy oil sample preparation
Abstract
A substantially solids-free sample of an oil having
substantially the same hydrocarbon distribution as a heavy oil
contained in a subterranean reservoir is prepared by vacuum-topping
a field sample of the oil or oil-containing material while
cold-trapping volatiles, diluting the topped oil with a volatile
oil solvent, mechanically separating the solution from entrained
solids, vacuum-distilling the solvent from the dissolved oil and
recombining the oil and the cold-trapped volatiles.
Inventors: |
Closmann; Philip J. (Houston,
TX), Wortham; James T. (Edna, TX) |
Assignee: |
Shell Oil Company (Houston,
TX)
|
Family
ID: |
23780722 |
Appl.
No.: |
06/448,542 |
Filed: |
December 10, 1982 |
Current U.S.
Class: |
436/175; 208/184;
208/186; 208/88; 436/177; 436/178 |
Current CPC
Class: |
G01N
33/2823 (20130101); Y10T 436/255 (20150115); Y10T
436/25375 (20150115); Y10T 436/25125 (20150115) |
Current International
Class: |
G01N
33/26 (20060101); G01N 33/28 (20060101); G01N
001/00 (); G01N 033/28 (); C10M 011/00 () |
Field of
Search: |
;203/47,73,91
;208/88,184,186,251R ;436/25,29,174,175,177,178 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Turk; Arnold
Assistant Examiner: Hill, Jr.; Robert J.
Claims
What is claimed is:
1. A process for preparing for laboratory utilizations a
substantially solids-free sample of a heavy reservoir oil in which
the hydrocarbon distribution is substantially the same as that in
the reservoir oil, comprising:
vacuum-distilling volatile components from a field sample of oil or
oil-containing material from a subterranean heavy oil reservoir at
a temperature which is at least significantly greater than the
boiling point of an oil solvent to be used for subsequently
dissolving the heavy hydrocarbon components of the reservoir oil
but is less than the boiling or cracking temperature of the heavy
hydrocarbon components of the reservoir oil while condensing and
retaining substantially all of the distillate;
mechanically separating water from hydrocarbon components of the
resultant condensate;
dissolving the remaining topped heavy hydrocarbon components of the
reservoir oil in a volatile oil solvent and mechanically freeing
the solution of substantially all solid particles having diameters
greater than about 0.1 micron;
distilling substantially all of the volatile oil solvent from the
solids-free solution at a temperature and pressure which is
significantly less than that used in the vacuum distillation of the
field sample; and
combining the condensed volatile hydrocarbon components with the
heavy hydrocarbon components from which solids have been removed to
provide a substantially solids-free sample of oil having a
hydrocarbon distribution substantially equalling that of the
reservoir oil.
2. The process of claim 1 in which the vacuum distillation of
volatile hydrocarbon components is conducted at a temperature of
about 70.degree. C. and a pressure of less than about 0.01
millimeter of mercury and the volatile oil solvent in which the
topped heavy hydrocarbon components of the reservoir oil are
dissolved contains at least one non-hydrocarbon group or atom and
is distilled from the solution at a temperature less than about
60.degree. C.
3. The process of claim 2 in which the volatile oil solvent is
methylene chloride and is distilled from the solution at about
50.degree. C.
Description
BACKGROUND OF THE INVENTION
This invention relates to extracting a heavy oil from a field
sample of the oil and/or oil-containing portion of a subterranean
oil formation and preparing a substantially solids-free oil sample
having a chemical composition which is substantially identical to
that of the oil in the reservoir.
As far as applicants have been able to ascertain, the methods of
separating such oils from field samples and preparing samples for
laboratory utilizations have remained substantially the same for at
lest about 40 years. For example, the textbook "Petroleum
Production Engineering Oil Field Development" by Lester Charles
Uren, McGraw-Hill Book Company, Inc., 1946, describes a procedure
for extracting oil from field samples. It comprises contacting the
sample in a Soxhlet extractor with substantially any volatile
solvent which does not alter the mineral structure of the reservoir
material and is capable of dissolving the oil or oil residue from
the reservoir material. In a booklet, "Syncrude Analytical Methods
for Oil Sand and Bitumen Processing", published by Syncrude Canada,
Ltd., August, 1979, the extraction procedure is substantially the
same--"The sample is separated into bitumen, water and solids by
refluxing with toluene in a solids extraction apparatus. Condensed
solid and co-distilled water are continuously separated in a trap,
the water being retained in the graduated section" (page 46).
Such prior procedures are relatively widely used but have a serious
defect. It is generally desirable to mechanically separate the
laboratory sample of the oil from solid particles large than about
0.1 micron; for example, by filtration through a millipore filter
or by means of centrifugation. Due to the high viscosity of heavy
oils, their dilution with the volatile solvent is usually required.
After separating the solid particles, the solvent is removed by
evaporation. The evaporation removes most of the water which is
present in the original oil and also removes most or all of the
volatile components that were present in the oil. Thus, in such
prior procedures, the light ends are irretrievably lost and the
hydrocarbon distribution within the solids-free sample of the oil
is different from that in the original oil. These differences are
particularly important in tests of the mobility of the oil in cores
or packs at different temperatures and/or in contact with different
fluids.
SUMMARY OF THE INVENTION
The present invention relates to a process for preparing a
substantially solids-free sample of a heavy oil obtaiined from a
subterranean reservoir formation so that the hydrocarbon
distribution in the solids-free oil is substantially the same as
that in the reservoir oil. As a first step, the volatile
hydrocarbon components are vacuum-distilled from a field sample of
oil or oil-containing material from the subterranean reservoir
formation. The distillation is conducted at a temperature which is
greater than the boiling point of the oil solvent to be used but
less than the boiling or cracking temperature of the heavy
hydrocarbon components of the reservoir oil. Substantially all of
the distilled light ends and water are condensed and retained.
Water is mechanically separated from the condensed volatile
hydrocarbon components. The "topped" heavy hydrocarbon components
of the reservoir oil, which remain as a distillation residue, are
dissolved in a volatile oil solvent and the solution is
mechanically separated from substantially all solid particles
having diameters greater than about 0.1 micron. Subtantially all of
the oil solvent is then vacuum-distilled from the solids-free
solution of the heavy hydrocarbon components of the reservoir oil.
The condensed volatile hydrocarbon components of the reservoir oil
are then combined with the solids-free heavy hydrocarbons,
remaining as a residue from the distillation of the solvent, in
order to form a reconstituted solids-free reservoir oil having
substantially the same hydrocarbon distribution as the oil in the
reservoir.
DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic illustration of an apparatus suitable for
vacuum-distilling the volatile components from a reservoir oil in
accordance with the present invention.
FIG. 2 is a graph of the weight percent of hydrocarbons with the
indicated numbers of carbon atoms.
DESCRIPTION OF PREFERRED EMBOIDMENTS
FIG. 1 shows an apparatus with which the volatile hydrocarbon
components or light ends can advantageously be vacuum-distilled
from a field sample of the reservoir oil or an oil-containing
portion of the subterranean reservoir formation. The field sample
is placed in distillation flask 1, which is arranged to be
mechanically rotated by a motor unit 2 while being evacuated by a
vacuum pump 3. The distillation flask is preferably heated in a
liquid-filled fluid bath 4. The volatilized light ends and any
water present in the field sample are preferably condensed in an
evacuated container immersed in a liquid-filled cold trap 5. Such a
cold trap is preferably cooled by liquid nitrogen, a mixture of
acetone and dry ice, or the like, to form a condensed liquid 6
comprising condensed "light" or volatile hydrocarbons and any water
that was present in the field sample.
The initial evacuation or distillation of the volatile hydrocarbon
and water components of the field sample can conveniently be
conducted in a distillation flask connected to a stirring and
evacuating system such as a Rotovac Unit available from Buchlar
Instruments. Such a vacuum distillation is preferably conducted at
a relatively "hard vacuum" at least as low as about 0.01 millimeter
of mercury. The distillation flask is preferably heated in a water
bath to a temperature of not more than about 70.degree. C. Where
the field sample is, or contains, portions of solid reservoir
formation material, that solid material is preferably crushed and
placed in the distillation flask along with heat transfer-material
such as relatively large steel balls.
After the vacuum-distillation of the volatile components of the
field sample, the residual material in the distillation flask is
contacted with a volatile oil solvent and dissolved and/or
dispersed to form a solution containing substantially all of the
heavy hydrocarbon components of reservoir oil. The volatile oil
solvent preferably comprises at least one liquid which is
substantially completely miscible with substantially all components
of the reservoir oil and contains non-hydrocarbon groups or atoms
and/or radioactive isotopes which are readiliy detectable in the
presence of hydrocarbons, for making it easy to detect the amount
of the solvent which is mixed with hydrocarbon components of the
reservoir oil. Halogenated hydrocarbon oil solvents such as
methylene chloride, chloroform, Freon-11(b.p. about 24.degree. C.)
and mixtures such as methanol and chloroform are suitable.
Methylene chloride is a particularly suitable solvent.
The resulting solution of heavy oil hydrocarbons in an oil solvent
is mechanically freed of solid particles by a mechanical means such
as filtration or centrifugation. The separation is preferably
accomplished by filtering the solution through a millipore filter
having pore sizes of about 0.1 micron. Such a separation can be
conducted by means of substantially any of the conventionally
available methods or apparatuses.
The volatile oil solvent in the resulting substantially solids-free
solution of heavy hydrocarbons is preferably distilled out of that
solution (for example, at a temperature no greater than about
50.degree. C. in the case of methylene chloride solvent) to an
extent reducing the solvent concentration in the solution to less
than about 0.1 percent by weight. In general, the temperature at
which the volatile oil solvent is distilled should be at least
about 10.degree. C. less than the temperature at which the volatile
components were distilled from the field sample. The heavy
hydrocarbons remaining after the distillation of the volatile oil
solvent are then mixed with the volatile hydrocarbons condensed in
the initial vacuum-distillation of the field sample to provide a
substantially solids-free sample of a reservoir oil having a
hydrocarbon distribution substantially equalling that of the oil in
the reservoir.
EXAMPLES:
The following example illustrates a reconstruction of the original
hydrocarbon distribution of a sample of Cat Canyon crude oil by
means of an initial evacuation, cold-tapping and recombination in
accordance with the present process. The hydrocarbon distributions
at each stage are shown in Table 1. As known to those skilled in
the art the exemplified results would be substantially unchanged by
the inclusion of the presently specified procedures of diluting the
initially evacuated, mechanically removing solids, distilling of
the solvent prior to the recombining of the light and heavy
components as exemplified.
The hydrocarbon distributions were obtained by a standard
"simulated boiling point" procedure. In that procedure a relatively
small sample in stripped with inert gas at a relatively high
temperature and the residue is burned while measurements are being
made of the proportions of each of the hydrocarbon fractions. The
results have a known correlation with the hydrocarbon distribution
that would be obtained by an actual distillation of a relatively
large sample.
TABLE 1 ______________________________________ Carbon B.P.,
.degree.C. Volatility Distribution, Weight Percent Number at 760 mm
Column A Column B Column C ______________________________________ 4
-0.5 -- -- -- 5 36.1 -- -- -- 6 68.7 0.4 0.0 0.6 7 98.4 1.3 0.0 0.8
8 125.7 2.1 0.0 1.4 9 150.8 2.3 0.0 1.8 10 174.1 2.1 0.0 1.9 11
195.9 2.2 0.3 2.0 12 216.3 2.1 1.1 1.9 13 235.4 2.3 1.6 2.3 14
253.6 2.1 1.8 2.1 15 270.6 1.9 1.8 1.9 16 286.8 1.7 1.6 1.6 17
301.8 1.9 1.8 1.8 18 316.1 1.7 1.7 1.7 19 329.7 1.4 1.4 1.3 20
342.7 1.3 1.3 1.3 21 355.6 1.2 1.2 1.2 22 367.6 1.1 1.1 1.2 23
379.0 1.1 1.1 1.1 24 389.9 0.9 1.0 1.0 25 400.4 0.9 1.0 1.0 26
410.5 0.8 1.0 1.0 27 420.2 0.8 1.0 1.0 28 429.6 0.8 1.0 1.0 29
438.6 0.8 1.0 1.0 30 447.3 0.8 1.0 0.9 31 456 0.7 0.9 0.9 32 464
0.7 0.8 0.8 33 472 0.6 0.8 0.8 34 479 0.6 0.7 0.7 >34 >479
61. 72. 62. ______________________________________
The hydrocarbon distribution of the original tar is listed in
Column A. After that tar was heated and subjected to evacuation at
a temperature of about 70.degree. C., its hydrocarbon distribution
was that shown in Column B. When the volatile hydrocarbon
components were recovered from the cold trap and added back to the
topped tar sample (having the composition shown in Column B) the
composition of the reconstituted tar is shown in Column C.
The tabulated results show that in the topped sample the C7 and C8
components are substantially missing and there is a significant
increase in the fraction of components heavier than C34. Such an
increase is typically produced by a loss of light ends. Column C
shows that the adding back of the cold-trapped volatiles
substantially reproduces the original hydrocarbon distribution of
the original sample.
FIG. 2 shows a graph of the results listed in Table 1. In the
exemplified procedure the volatile hydrocarbon components cold
trapped at the temperature of an acetone/dry ice bath. As shown in
FIG. 2, the volatility distribution is completely different for the
original and that oil after the light ends were removed, up to
carbon numbers of about 15. The reconstituted oil, however, has
most of the missing fractions. It is possible that, even with the
procedure exemplified, a trace of light ends can be lost. This
could be minimized by using a liquid nitrogen cold trap or other
trap of lower temperature.
To illustrate the effect of the light ends on the overall
viscosity, it should be noted that a crude such as that shown in
FIG. 2 would have a viscosity of about 2300 centipoises at
75.degree. F. If about 12% of the light ends are lost due to an
inadequate condensation of the initially vaporized light ends (as
discussed above and indicated in FIG. 2), and/or due to
vaporization with solvent removal, the residue would probably have
a viscosity of at least 9000 centipoises. Such a marked difference
in viscosity could considerably affect the flow properties of the
recovered material.
Such viscosity differences may be important. Although different
crude oils are sometimes considered to be similar if their API
gravities are similar (and thus may be expected to have similar
flow properties) there is surprisingly little correlation between a
high API gravity and a low viscosity. A plot showing the trend of
API gravity with oil viscosity is given in "Laboratory Test on
Heavy Oil Recovery by Steam Injection", SPE Paper No. 10778,
presented at the 1982 California Regional Meeting of SPE, Mar.
24-26, 1982, by P. J. Closmann and R. D. Seba.
* * * * *